WO2020250621A1 - 接着剤及び接着方法 - Google Patents

接着剤及び接着方法 Download PDF

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Publication number
WO2020250621A1
WO2020250621A1 PCT/JP2020/019519 JP2020019519W WO2020250621A1 WO 2020250621 A1 WO2020250621 A1 WO 2020250621A1 JP 2020019519 W JP2020019519 W JP 2020019519W WO 2020250621 A1 WO2020250621 A1 WO 2020250621A1
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WIPO (PCT)
Prior art keywords
mass
parts
chloroprene
adhesive
chloroprene copolymer
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PCT/JP2020/019519
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English (en)
French (fr)
Japanese (ja)
Inventor
直樹 関岡
渋谷　彰
展子 尾川
凌 牧尾
Original Assignee
昭和電工株式会社
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Application filed by 昭和電工株式会社 filed Critical 昭和電工株式会社
Priority to EP20823361.9A priority Critical patent/EP3985076A4/de
Priority to JP2021525956A priority patent/JP7409377B2/ja
Priority to US17/618,114 priority patent/US20220243101A1/en
Priority to CN202080041740.3A priority patent/CN113993963B/zh
Publication of WO2020250621A1 publication Critical patent/WO2020250621A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J111/00—Adhesives based on homopolymers or copolymers of chloroprene
    • C09J111/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/383—Natural or synthetic rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2311/00—Characterised by the use of homopolymers or copolymers of chloroprene
    • C08J2311/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2411/00—Presence of chloroprene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/10—Presence of homo or copolymers of propene
    • C09J2423/106—Presence of homo or copolymers of propene in the substrate

Definitions

  • the present invention relates to an adhesive and an adhesive method.
  • Chloroprene copolymers can obtain high adhesive strength with low pressure bonding to various types of adherends. It is suitably used for adhesive applications such as organic solvent-based adhesives.
  • adhesive applications such as organic solvent-based adhesives.
  • VOC volatile organic compound
  • organic solvent regulations organic solvent regulations
  • Water-based adhesives containing polymer latex have been proposed.
  • Patent Document 1 proposes an aqueous adhesive containing a latex of a copolymer of chloroprene, ⁇ , ⁇ -unsaturated carboxylic acid, and 2,3-dichloro-1,3-butadiene.
  • the adhesive strength heat resistance
  • the water-based adhesive disclosed in Patent Document 1 has a problem that the adhesive strength is lower than that of the conventional organic solvent-based adhesive.
  • Patent Document 2 proposes an aqueous adhesive using a latex of a chloroprene copolymer that does not contain an organic solvent-insoluble component
  • Patent Document 3 proposes a predetermined amount of an organic solvent-insoluble component and a predetermined molecular weight.
  • An aqueous adhesive using a latex of a chloroprene copolymer containing an organic solvent-soluble component has been proposed.
  • An object of the present invention is to solve the above-mentioned problems of the prior art and to provide an aqueous adhesive and an adhesive method that exhibit high adhesive force to polyolefin.
  • the chloroprene copolymer (A) contains chloroprene (A-1), ⁇ , ⁇ -unsaturated carboxylic acid (A-2), and 2,3-dichloro-1,3-butadiene (A-3).
  • the chloroprene copolymer (A) has a unit derived from the chloroprene (A-1) of 80.0 parts by mass or more and 99.4 parts by mass.
  • the unit derived from the ⁇ , ⁇ -unsaturated carboxylic acid (A-2) is 0.5 parts by mass or more and 10.0 parts by mass or less
  • the 2,3-dichloro-1,3-butadiene (A) has a unit derived from -3) of 0.1 parts by mass or more and 4.0 parts by mass or less.
  • the chloroprene copolymer (A) has a tetrahydrofuran-soluble component soluble in tetrahydrofuran, and the weight average molecular weight of the tetrahydrofuran-soluble component is 80,000 or more and 140,000 or less.
  • the content of the metal oxide (B) is such that the amount of the metal oxide (B) is Y parts by mass with respect to 100 parts by mass of the chloroprene copolymer (A), and the weight average molecular weight of the tetrahydrofuran-soluble component is used.
  • the chloroprene copolymer (A) has a gel insoluble in tetrahydrofuran, and the content of the gel in the chloroprene copolymer (A) is 0.1% by mass or more and less than 15% by mass [ The adhesive according to any one of 1] to [4]. [6] The adhesive according to any one of [1] to [5], wherein the chloroprene copolymer latex contains an emulsifier. [7] The adhesive according to [6], wherein the emulsifier is partially saponified polyvinyl alcohol.
  • the adhesive according to the embodiment of the present invention is an adhesive containing a chloroprene copolymer latex containing a chloroprene copolymer (A) and a metal oxide (B).
  • the chloroprene copolymer (A) contains chloroprene (A-1), ⁇ , ⁇ -unsaturated carboxylic acid (A-2) and 2,3-dichloro-1,3-butadiene (A-3). It is a copolymer of the monomer group.
  • the chloroprene copolymer (A) has a unit derived from the chloroprene (A-1) of 80.0 parts by mass or more and 99.4 parts by mass.
  • the unit derived from ⁇ , ⁇ -unsaturated carboxylic acid (A-2) is 0.5 parts by mass or more and 10.0 parts by mass or less, 2,3-dichloro-1,3-butadiene (A-3). It has a unit derived from 0.1 parts by mass or more and 4.0 parts by mass or less.
  • the chloroprene copolymer (A) has a tetrahydrofuran-soluble component soluble in tetrahydrofuran, and the weight average molecular weight of the tetrahydrofuran-soluble component is 80,000 or more and 140,000 or less.
  • the chloroprene copolymer (A) preferably has a gel insoluble in tetrahydrofuran, and the content of the gel in the chloroprene copolymer (A) is 0.1% by mass or more and less than 15% by mass. preferable.
  • the content of the metal oxide (B) in the adhesive according to the present embodiment is such that the amount of the metal oxide (B) with respect to 100 parts by mass of the chloroprene copolymer (A) is Y parts by mass and a tetrahydrofuran-soluble component.
  • the weight average molecular weight of is X, the formula of ⁇ 1.2 ⁇ X / 1000000 + 1.6 ⁇ Y ⁇ -4.2 ⁇ X / 1000000 + 5.7 is satisfied.
  • Such an adhesive according to the present embodiment is a water-based adhesive that does not contain an organic solvent and exhibits high adhesive strength to polyolefin. Therefore, the adhesive according to the present embodiment is suitable for adhering an adherend made of polyolefin. That is, even if at least one of the two adherends to be adhered is made of polyolefin, which is a material that is difficult to adhere, for example, it exhibits a high adhesive force of 0.7 kN / m or more. Two adherends can be glued together. However, the adhesive according to this embodiment can also be applied to the adhesion of an adherend made of a material other than polyolefin.
  • the form of the adherend is not particularly limited, and the adhesive according to the present embodiment can be used for adhering foams, sheets, films and the like.
  • the adhesive in the present invention also includes an adhesive.
  • the adhesive and the bonding method according to the present embodiment will be described in more detail below.
  • the adhesive according to the present embodiment contains latex, and this latex is a chloroprene copolymer latex containing a chloroprene copolymer (A).
  • the chloroprene copolymer (A) contains chloroprene (A-1), ⁇ , ⁇ -unsaturated carboxylic acid (A-2), and 2,3-dichloro-1,3-butadiene (A-3). It is a copolymer of the contained monomer group.
  • ⁇ , ⁇ -unsaturated carboxylic acid (A-2) ⁇ , ⁇ -unsaturated carboxylic acid (A-2), which is one monomer of the chloroprene copolymer (A), is contained in the molecule. It is a carboxylic acid having a reactive double bond.
  • the type of ⁇ , ⁇ -unsaturated carboxylic acid (A-2) is not particularly limited, and examples thereof include methacrylic acid, acrylic acid, itaconic acid, 2-ethylmethacrylic acid, and 2-butylacrylic acid. be able to. Of these, methacrylic acid is more preferred.
  • the ⁇ , ⁇ -unsaturated carboxylic acid (A-2) one type may be used alone, or two or more types may be used in combination.
  • A-3 About 2,3-dichloro-1,3-butadiene (A-3) 2,3-dichloro-1,3-butadiene (A-3) is one single amount of the chloroprene copolymer (A). It is a body and copolymerizes with other monomers such as chloroprene (A-1) and ⁇ , ⁇ -unsaturated carboxylic acid (A-2) to produce a chloroprene copolymer (A).
  • the chloroprene copolymer (A) is chloroprene (A-1), ⁇ , ⁇ -unsaturated carboxylic acid (A-2), and 2,3-. It may be a copolymer of three kinds of monomers of dichloro-1,3-butadiene (A-3), but chloroprene (A-1), ⁇ , ⁇ -unsaturated carboxylic acid (A-2). , 2,3-Dichloro-1,3-butadiene (A-3) may be a copolymer obtained by copolymerizing a fourth monomer (A-4) which is another monomer.
  • the chloroprene copolymer (A) includes chloroprene (A-1), ⁇ , ⁇ -unsaturated carboxylic acid (A-2), 2,3-dichloro-1,3-butadiene (A-3), and It may be a copolymer of a group of monomers composed of a fourth monomer (A-4).
  • the fourth monomer (A-4) is chloroprene (A-1), ⁇ , ⁇ -unsaturated carboxylic acid (A-2), and 2,3-dichloro-1,3-butadiene (A-). It is necessary to have reactivity capable of copolymerization with 3).
  • the type of the fourth monomer (A-4) is not particularly limited as long as it has the above reactivity, but for example, 1-chloro-1,3-butadiene, butadiene, isoprene, and styrene. , Acrylonitrile, acrylic acid ester, methacrylic acid ester and the like.
  • the fourth monomer (A-4) one kind of monomer may be used alone, or two or more kinds of monomers may be used in combination.
  • Chloroprene copolymer (A) contains chloroprene (A-1), ⁇ , ⁇ -unsaturated carboxylic acid (A-2) and 2,3-dichloro-1,3. It is a copolymer of a monomer group containing at least -butadiene (A-3), and among the units constituting the chloroprene copolymer (A), the unit derived from chloroprene (A-1) is used.
  • the unit derived from chloroprene (A-1) is preferably 85.0 parts by mass or more and 98.0 parts by mass or less, and more preferably 88.0 parts by mass or more and 96.0 parts by mass or less.
  • the unit derived from ⁇ , ⁇ -unsaturated carboxylic acid (A-2) is preferably 2.0 parts by mass or more and 8.0 parts by mass or less, and 3.0 parts by mass or more and 7.5 parts by mass or less. More preferably.
  • the unit derived from 2,3-dichloro-1,3-butadiene (A-3) is preferably 0.5 parts by mass or more and 10.0 parts by mass or less, and 0.75 parts by mass or more and 5.0 parts by mass or less. More preferably, it is less than or equal to a part.
  • the adhesive strength of the adhesive is sufficiently high. Further, if the unit derived from ⁇ , ⁇ -unsaturated carboxylic acid (A-2) is 10.0 parts by mass or less, agglutination is unlikely to occur in the chloroprene copolymer latex and it remains after polymerization. The amount of ⁇ , ⁇ -unsaturated carboxylic acid (A-2) is small. When the amount of ⁇ , ⁇ -unsaturated carboxylic acid (A-2) remaining after the polymerization is small, the odor of the adhesive is small, and the adhesive strength and adhesive strength of the adhesive are sufficiently high.
  • the adhesive strength of the adhesive is sufficiently high. Further, if the unit derived from 2,3-dichloro-1,3-butadiene (A-3) is 4.0 parts by mass or less, the crystallinity of the chloroprene copolymer (A) becomes low, so that the adhesive Adhesive strength is high enough.
  • the chloroprene copolymer (A) is chloroprene (A-1), ⁇ , ⁇ -unsaturated carboxylic acid (A-2), 2,3-dichloro-1,3-butadiene (A-3), and the fourth.
  • the content of the fourth monomer (A-4) is not particularly limited, but the chloroprene is also used.
  • the polymer (A) contains 80.0 parts by mass or more and 99.4 parts by mass or less of the unit derived from chloroprene (A-1), ⁇ , ⁇ -.
  • the unit derived from the unsaturated carboxylic acid (A-2) is 0.5 parts by mass or more and 10.0 parts by mass or less, and the unit derived from 2,3-dichloro-1,3-butadiene (A-3) is 0. It is preferable to have 1 part by mass or more and 4.0 parts by mass or less, and the unit derived from the fourth monomer (A-4) is more than 0.0 parts by mass and 10.0 parts by mass or less. When the unit derived from the fourth monomer (A-4) exceeds 0.0 parts by mass and 10.0 parts by mass or less, the adhesive strength and adhesive strength of the adhesive tend to be higher.
  • the chloroprene copolymer (A) is chloroprene (A-1), ⁇ , ⁇ -unsaturated carboxylic acid (A-2), 2,3-dichloro-1,3-butadiene (A-3), and
  • the unit derived from chloroprene (A-1) is 85.0 parts by mass or more and 97.0 parts by mass. It is more preferably 94.0 parts by mass or more, and further preferably 97.0 parts by mass or less.
  • the unit derived from ⁇ , ⁇ -unsaturated carboxylic acid (A-2) is more preferably 1.0 part by mass or more and 5.0 part by mass or less, and 2.0 parts by mass or more and 4.0. It is more preferably parts by mass or less.
  • the unit derived from 2,3-dichloro-1,3-butadiene (A-3) is more preferably 0.3 parts by mass or more and 3.0 parts by mass or less, and more preferably 0.5 parts by mass or more. It is more preferably 2.0 parts by mass or less.
  • the unit derived from the fourth monomer (A-4) is more preferably 0.1 parts by mass or more and 7.0 parts by mass or less, and 0.5 parts by mass or more and 5.0 parts by mass or less. The following is more preferable.
  • the chloroprene copolymer (A) preferably has a gel insoluble in tetrahydrofuran and a tetrahydrofuran-soluble component soluble in tetrahydrofuran.
  • the weight average molecular weight of the tetrahydrofuran-soluble component is 80,000 or more and 140,000 or less.
  • the gel content in the chloroprene copolymer (A) is preferably 0.1% by mass or more and less than 15.0% by mass.
  • the gel in the present invention is a component of the chloroprene copolymer (A) that is insoluble in tetrahydrofuran.
  • the content of the gel in the chloroprene copolymer (A) is preferably 0.3% by mass or more and 10.0% by mass or less, and more preferably 0.5% by mass or more and 8.0% by mass or less. preferable.
  • the weight average molecular weight of the tetrahydrofuran-soluble component is preferably 85,000 or more and 136,000 or less, more preferably 90,000 or more and 136,000 or less, and 90,000 or more and 11. It is more preferably 0,000 or less.
  • the weight average molecular weight of the tetrahydrofuran-soluble component may be less than 100,000.
  • the strength of the adhesive (for example, the adhesive formed in the form of a film) becomes sufficiently high.
  • the adhesive strength of the adhesive becomes sufficiently high (for example, 0.4 kN / m or more).
  • the weight average molecular weight (Mw) of the tetrahydrofuran-soluble component is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (hereinafter referred to as “GPC”).
  • the solution phase was separated in the same manner as in the method for measuring the gel content in the chloroprene copolymer (A), and this solution phase was diluted with tetrahydrofuran.
  • the solution is subjected to GPC measurement.
  • the chloroprene copolymer (A) is emulsified by an emulsifier and dispersed in water as particles.
  • the particles of the chloroprene copolymer (A) are dispersed in water by an emulsifier, and chloroprene (A-1) and ⁇ , ⁇ -unsaturated carboxylic acid ( ⁇ , ⁇ -unsaturated carboxylic acid) ( By emulsifying radical polymerization of A-2), 2,3-dichloro-1,3-butadiene (A-3) and, if desired, a fourth monomer (A-4) in an aqueous medium. Obtainable.
  • the pH of the chloroprene copolymer latex of the present embodiment is preferably 4.5 or more and 8.5 or less, more preferably 5.0 or more and 8.5 or less, and 6.0 or more and 8 or less at 25 ° C. It is more preferably 0.0 or less.
  • a pH adjuster may be added to the chloroprene copolymer latex in order to keep the pH of the chloroprene copolymer latex within the above range.
  • Preferred examples of the pH adjuster include acids and bases, and amines such as diethanolamine and triethanolamine are more preferable.
  • the solid content concentration of the chloroprene copolymer latex of the present embodiment is preferably 35% by mass or more and 65% by mass or less, more preferably 37% by mass or more and 60% by mass or less, and 40% by mass or more and 55% by mass. It is more preferably% or less.
  • the solid content concentration is within the above range, it is possible to reduce the drying time of the chloroprene copolymer latex and reduce the load on the drying device of the chloroprene copolymer latex.
  • the solid content concentration is within the above range, it becomes easier to maintain the colloidal stability of the particles of the chloroprene copolymer (A) in the chloroprene copolymer latex, and the generation of agglomerates is minimized. Can be fastened.
  • the chloroprene copolymer latex contains chloroprene (A-1), ⁇ , ⁇ -unsaturated carboxylic acid (A-2), and 2,3. -Dichloro-1,3-butadiene (A-3) and, if desired, a fourth monomer (A-4) can be obtained by emulsifying radical polymerization in an aqueous medium.
  • the gel content of the chloroprene copolymer (A) produced by the emulsion radical polymerization and the weight average molecular weight of the tetrahydrofuran-soluble component are the types of emulsifiers, chain transfer agents, polymerization initiators and polymerization terminators used for the emulsion radical polymerization. It can be controlled by the polymerization conditions of emulsion radical polymerization (for example, polymerization conversion rate, polymerization temperature).
  • the type of emulsifier is not particularly limited, but since ⁇ , ⁇ -unsaturated carboxylic acid (A-2) is water-soluble, an emulsifier capable of emulsifying even at a low pH can be used.
  • anionic emulsifiers include dodecylbenzenesulfonates such as sodium dodecylbenzenesulfonic acid and triethanolamine dodecylbenzenesulfonic acid, and diphenylethersulfonates such as sodium diphenylethersulfonic acid and ammonium diphenylethersulfonic acid.
  • naphthalene sulfonates such as sodium salt of ⁇ -naphthalene sulfonic acid formaldehyde condensate.
  • nonionic emulsifier examples include polyvinyl alcohol, partially saponified polyvinyl alcohol, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene lauryl ether and the like.
  • partially saponified polyvinyl alcohol is more preferable because it has good colloidal stability during storage of the chloroprene copolymer latex and the adhesive, and bleed-out of the surfactant is unlikely to occur after drying.
  • the emulsifier one type may be used alone, or two or more types may be used in combination.
  • the amount of the emulsifier used in the emulsion radical polymerization is not particularly limited, but it is preferably used in the range of 1.0 part by mass or more and 8.0 part by mass or less with respect to 100 parts by mass of the total amount of all the monomers. , It is more preferable to use it in the range of 1.5 parts by mass or more and 6.0 parts by mass or less, and further preferably it is used in the range of 2.0 parts by mass or more and 5.0 parts by mass or less.
  • the amount of the emulsifier used is 1.0 part by mass or more, a sufficiently good emulsified state can be obtained, so that the heat of polymerization is controlled and problems such as the formation of agglomerates and poor appearance of the product are unlikely to occur.
  • the amount of the emulsifier used is 8.0 parts by mass or less, the emulsifier does not easily remain, so that the water resistance of the chloroprene copolymer (A) is lowered, the adhesive strength and the adhesive strength are lowered, and foaming during drying occurs. Problems such as deterioration of product color are unlikely to occur.
  • chain transfer agent is not particularly limited, but xanthate disulfide, thioglycolic acid ester, and alkyl mercaptan can be used. Specific examples include diisopropylxanthogen disulfide, diethylxantogen disulfide, dicyclohexylxanthogen disulfide, dilaurylxantogen disulfide, dibenzylxantogen disulfide, methyl thioglycolate, 2-ethylhexyl thioglycolate, methoxybutyl thioglycolate, n-dodecyl mercaptan, Examples thereof include n-decyl mercaptan and octyl mercaptan. These chain transfer agents may be used alone or in combination of two or more.
  • the type of polymerization initiator is not particularly limited, but a general radical polymerization initiator can be used.
  • organic peroxides such as benzoyl peroxide and tert-butyl hydroperoxide
  • inorganic peroxides such as potassium persulfate and ammonium persulfate
  • azo compounds such as azobisisobutyronitrile are used. used.
  • the polymerization initiator one type may be used alone, or two or more types may be used in combination.
  • a co-catalyst such as anthraquinone sulfonate, potassium sulfite, and sodium sulfite may be used in combination with the polymerization initiator as appropriate.
  • a co-catalyst one type may be used alone, or two or more types may be used in combination.
  • a polymerization inhibitor may be added to terminate the reaction when a predetermined polymerization rate is reached.
  • the type of polymerization inhibitor is not particularly limited, but for example, phenothiazine, para-t-butylcatechol, hydroquinone, hydroquinone monomethyl ether, diethylhydroxylamine and the like can be used.
  • One type of polymerization inhibitor may be used alone, or two or more types may be used in combination.
  • the polymerization conversion rate in producing the chloroprene copolymer (A) of the present embodiment is not particularly limited, but is preferably 90% or more, more preferably 95% or more, and 98%. The above is more preferable. If the polymerization conversion rate is 90% or more, the solid content concentration of the chloroprene copolymer latex becomes a sufficient concentration, which causes a problem that the drying process after applying the adhesive to the adherend is burdened and the adhesive. Is unlikely to cause a problem that makes it difficult to form a film having a uniform thickness. Further, the problem of deterioration of the adhesive strength and the adhesive strength of the adhesive is unlikely to occur.
  • the polymerization temperature at the time of producing the chloroprene copolymer (A) of the present embodiment is not particularly limited, but is preferably 30 ° C. or higher and 60 ° C. or lower, and 35 ° C. or higher and 55 ° C. or lower. Is more preferable, and the temperature is more preferably 40 ° C. or higher and 50 ° C. or lower.
  • the polymerization temperature is 30 ° C. or higher, the productivity of the chloroprene copolymer (A) tends to be high, and the adhesive strength of the adhesive tends to be sufficient.
  • the polymerization temperature is 60 ° C.
  • the vapor pressure of chloroprene (A-1) is unlikely to increase during polymerization, so that the polymerization operation can be easily performed and the obtained chloroprene copolymer (A) can be obtained.
  • Mechanical properties such as tensile strength tend to be sufficiently high.
  • the adhesive of the present embodiment contains a chloroprene copolymer latex and a metal oxide (B).
  • the content of the metal oxide (B) in the adhesive of the present embodiment is as follows. That is, the content of the metal oxide (B) is when the amount of the metal oxide (B) is Y parts by mass and the weight average molecular weight of the tetrahydrofuran-soluble component is X with respect to 100 parts by mass of the chloroprene copolymer (A). In addition, it is an amount that satisfies the formula of ⁇ 1.2 ⁇ X / 1000000 + 1.6 ⁇ Y ⁇ -4.2 ⁇ X / 1000000 + 5.7.
  • the above formula is preferably ⁇ 1.5 ⁇ X / 1000000 + 2.0 ⁇ Y ⁇ -3.7 ⁇ X / 1000000 + 5.0, preferably ⁇ 3.4 ⁇ X / 1000000 + 4.0 ⁇ Y ⁇ -5.1. More preferably, it is ⁇ X / 100,000 + 6.1.
  • the adhesive containing the metal oxide (B) having a content satisfying the above formula has excellent adhesive strength because the carboxy group of the chloroprene copolymer (A) and the metal oxide (B) are ion-crosslinked. It exhibits high adhesive strength (for example, 0.7 kN / m or more) to polyolefins such as polyethylene and polypropylene. Therefore, even if at least one of the two adherends to be adhered is made of polyolefin, which is a material that is difficult to adhere, the adhesive of the present embodiment is interposed between the two adherends. By allowing the two adherends to be strongly adhered to each other.
  • the two adherends to be adhered can be strongly adhered to each other.
  • the adherend formed of the porous material include a porous body made of polyolefin such as polyethylene and polypropylene.
  • the adherend is porous, it is preferable because the surface of the adherend is uneven.
  • the amount of ionic cross-linking between the carboxy group of the chloroprene copolymer (A) and the metal oxide (B) is an appropriate amount. Therefore, the adhesive strength of the adhesive is excellent. Further, since the colloidal stability of the particles of the chloroprene copolymer (A) in the chloroprene copolymer latex is improved, the thickening of the adhesive is unlikely to occur. Further, the strength of the adhesive (for example, the adhesive formed in a film shape) becomes sufficiently high.
  • the type of metal oxide (B) is not particularly limited, and examples thereof include zinc oxide, magnesium oxide, lead oxide, trilead tetroxide, and antimony trioxide.
  • One of these metal oxides (B) may be used alone, or two or more thereof may be used in combination.
  • zinc oxide is preferable because it easily crosslinks with the carboxy group of the chloroprene copolymer (A).
  • the adhesive of the present embodiment can be produced by adding a powder of a metal oxide (B) to a chloroprene copolymer latex and mixing it.
  • a powder of a metal oxide (B) When the powder of the metal oxide (B) is insoluble in water, or when the powder of the metal oxide (B) destabilizes the colloidal state of the chloroprene copolymer (A), the metal oxide (B) It is preferable to prepare a dispersion (slurry) in which the powder of the above is dispersed in water in advance, add this dispersion to the chloroprene copolymer latex, and mix the mixture.
  • the volume average particle diameter measured by the dynamic light scattering method of the metal oxide (B) is preferably 10.0 ⁇ m or less, more preferably 1.0 ⁇ m or less, and 0.5 ⁇ m or less. Is even more preferable. When the volume average particle diameter of the metal oxide (B) is 10.0 ⁇ m or less, the particles of the metal oxide (B) are less likely to settle, and the dispersibility after blending with the chloroprene copolymer latex is excellent.
  • the volume average particle size of the metal oxide (B) can be measured by a dynamic light scattering method using a zetasizer nano S manufactured by Malvern Panalical.
  • the adhesive of the present embodiment can be formed only of the chloroprene copolymer latex and the metal oxide (B), but as long as the object of the present invention is not impaired, it can be received as necessary.
  • Additives such as acids, antioxidants, fillers, tackifiers, pigments, dyes, colorants, wetting agents, defoamers, thickeners and the like may be included.
  • a tackifier may be contained for the purpose of improving the adhesive strength.
  • the type of the tackifier is not particularly limited, and examples thereof include phenolic resins, terpene resins, rosin derivative resins, and petroleum hydrocarbons.
  • Specific examples of the tackifier include hydrogenated rosin, pentaerythritol ester of hydrogenated rosin, polymerized rosin, rosin-modified resin containing rosin as a main component, alkylphenol resin, rosin-modified phenol resin, terpene-modified phenol resin, and natural terpene resin. Can be mentioned.
  • One type of tackifier may be used alone, or two or more types may be used in combination.
  • the blending amount of the tackifier is preferably 10 parts by mass or more and 60 parts by mass or less, more preferably 20 parts by mass or more and 55 parts by mass or less, and 25 parts by mass or more and 50 parts by mass with respect to 100 parts by mass of the solid content of the chloroprene copolymer latex. It is more preferably parts by mass or less.
  • the method of blending the tackifier is not particularly limited, but the tackifier can be added to the chloroprene copolymer latex in the form of an emulsion in which the tackifier is emulsified and dispersed.
  • Example 1 (1) Preparation of chloroprene copolymer latex In a reactor having an internal volume of 3 L, 960 g of chloroprene (manufactured by Showa Denko Co., Ltd.), 32.5 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2,3-dichloro-1, 3-butadiene (manufactured by Showa Denko Co., Ltd.) 7.5 g, polyvinyl alcohol (emulsion, trade name PVA-205 manufactured by Kuraray Co., Ltd.) 41 g, N-lauroylethanolamide (trade name manufactured by Toho Chemical Industry Co., Ltd.) Toho Hall (registered trademark) ) N-230) 6 g, n-dodecyl mercaptan (chain transfer agent, manufactured by Tokyo Chemical Industry Co., Ltd.) 9 g, 2-
  • diethanolamine manufactured by Nippon Shokubai Co., Ltd.
  • the pH at 25 ° C. before the pH adjustment was 3.7
  • the pH at 25 ° C. after the pH adjustment was 7.4
  • the solid content concentration was 45.6% by mass.
  • the dispersion medium is water) 0.2 g, the tackifier terpenphenol resin emulsion (trade name Tamanol E-100 manufactured by Arakawa Chemical Industry Co., Ltd., solid content concentration 52% by mass) 11.5 g, wetting agent (San Nopco Co., Ltd.) 0.2 g of product name Nopco Wet 50) and 0.03 g of thickener (trade name SN Sixer 612 manufactured by San Nopco Co., Ltd.) were added and stirred well to obtain an adhesive.
  • the tackifier terpenphenol resin emulsion trade name Tamanol E-100 manufactured by Arakawa Chemical Industry Co., Ltd., solid content concentration 52% by mass
  • wetting agent San Nopco Co., Ltd.
  • 0.03 g of thickener trade name SN Sixer 612 manufactured by San Nopco Co., Ltd.
  • Table 1 summarizes the amounts of each raw material used in the preparation of the chloroprene copolymer latex and the production of the adhesive.
  • the unit of the amount of each raw material used in Table 1 is a mass part. Further, the amounts of the chloroprene copolymer (chloroprene copolymer in the chloroprene copolymer latex), zinc oxide, and the tackifier used in the production of the adhesive are shown as solid contents.
  • Examples 2 to 8 and Comparative Examples 1 to 16 Examples except that the amounts of chloroprene, methacrylic acid, 2,3-dichloro-1,3-butadiene, n-dodecyl mercaptan, and 2-ethylhexyl thioglycolate were changed as shown in Tables 1 and 2. The same operation as in No. 1 was carried out to prepare the chloroprene copolymer latex of Examples 2 to 8 and Comparative Examples 1 to 16. Then, the same operations as in Example 1 were carried out except that the amount of zinc oxide used was changed as shown in Tables 1 and 2, and the adhesives of Examples 2 to 8 and Comparative Examples 1 to 16 were applied. Manufactured.
  • the chloroprene copolymer latex is dried by heating at 141 ° C. for 30 minutes to give only the solid content. Then, the solid content concentration of the chloroprene copolymer latex is calculated from the mass of the chloroprene copolymer latex before heating and the mass of the solid content obtained by heating.
  • the solid content concentration of the chloroprene polymer latex is measured according to the above, and the measured value of this solid content concentration is defined as S.
  • the solid content concentration (theoretical value) when all of the monomers are polymerized, that is, when the polymerization reaction proceeds 100% is theoretically calculated, and this theoretical value is defined as T 100 .
  • the solid content concentration (theoretical value) when the monomer is not polymerized at all, that is, when the polymerization reaction proceeds by 0% is theoretically calculated, and this theoretical value T 0 is used.
  • the mass of this dry matter is the mass of the tetrahydrofuran-soluble component of the chloroprene copolymer, subtract the mass of the tetrahydrofuran-soluble component from the mass of the chloroprene copolymer, and use that value as the mass of the gel to obtain chloroprene. Calculate the gel content in the copolymer. Since the mass of the chloroprene copolymer (A) is almost the same as the mass of the solid content of the chloroprene copolymer latex, that value can be used.
  • the particle size of the filler is 10 ⁇ m
  • the column temperature is 40 ° C.
  • the flow velocity is 0.4 mL / min.
  • a polypropylene natural color plate (length 200 mm, width 25 mm, thickness 1 mm) is placed on a cotton canvas coated with an adhesive, and the cotton canvas and the polypropylene natural color plate are pressure-bonded at 23 ° C., and this is a test piece. And said. Then, after bonding, the test piece was cured for 3 days in an environment of a temperature of 23 ° C. and a relative humidity of 60% RH, and then a 180 ° peeling test specified in JIS K6854-2: 1999 was performed to obtain a normal adhesive strength (kN). / M) was measured. In addition, the peeled portion of the test piece after the 180 ° peeling test was observed to evaluate whether the peeling mode was cohesive fracture or interfacial fracture.
  • interfacial fracture represents a state of peeling at the interface between the polypropylene natural color plate and the adhesive layer, and occurs when the adhesive force to the adherend is smaller than the strength of the adhesive layer.
  • cohesive failure represents a state in which the adhesive layer is broken and peeled off, and occurs when the adhesive force to the adherend exceeds the strength of the adhesive layer, and the adherend has high strength. It is an ideal peeling state for bonding to each other.
  • Tables 1 and 2 show the evaluation results of the chloroprene copolymer latex and the adhesive. Further, FIG. 1 shows a graph showing the relationship between the amount Y of the metal oxide and the weight average molecular weight X of the tetrahydrofuran-soluble component in the adhesives of Examples 1 to 8 and Comparative Examples 1 to 16. The plots marked with ⁇ in the graph of FIG. 1 show examples, and the plots marked with ⁇ show comparative examples.
  • the content of the metal oxide is such that the amount of the metal oxide with respect to 100 parts by mass of the chloroprene copolymer is Y parts by mass and the weight average molecular weight of the tetrahydrofuran-soluble component is X. Satisfies the equation ⁇ 1.2 ⁇ X / 1000000 + 1.6 ⁇ Y ⁇ -4.2 ⁇ X / 1000000 + 5.7. Therefore, the adhesives of Examples 1 to 8 have a high adhesive strength to polypropylene of 0.77 to 1.16 kN / m (see Table 1). Therefore, the adhesives of Examples 1 to 8 are suitable as adhesives for adhering polypropylene.
  • the adhesives of Comparative Examples 1 to 3 since the weight average molecular weight of the tetrahydrofuran-soluble component exceeds 140,000, the adhesive strength to polypropylene is as low as less than 0.5 kN / m, and the adhesive strength is insufficient. Met. Further, the adhesives of Comparative Examples 4 to 9 in which the content of the metal oxide does not satisfy the above formula and satisfies the formula ⁇ 1.2 ⁇ X / 1000000 + 1.6> Y, and Y> -4.2 ⁇ . The adhesives of Comparative Examples 10 to 13 satisfying the formula of X / 1000000 + 5.7 had a low adhesive strength to polypropylene of 0.65 kN / m or less, and the adhesive strength was insufficient.
  • the adhesives of Comparative Examples 14 and 15 were ⁇ , ⁇ -unsaturated carboxylic acids (A-2) in the chloroprene copolymer (A) when the amount of the chloroprene copolymer (A) was 100 parts by mass. Since the unit derived from is more than 10 parts by mass, the adhesive force to polypropylene is as low as less than 0.5 kN / m, and the adhesive force is insufficient. Since the adhesive of Comparative Example 16 does not have a unit derived from 2,3-dichloro-1,3-butadiene (A-3) in the chloroprene copolymer (A), the adhesive strength to polypropylene is 0.5 kN. It was as low as less than / m, and the adhesive strength was insufficient.
  • A-2 2,3-dichloro-1,3-butadiene

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PCT/JP2020/019519 2019-06-12 2020-05-15 接着剤及び接着方法 WO2020250621A1 (ja)

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US17/618,114 US20220243101A1 (en) 2019-06-12 2020-05-15 Adhesive agent and adhesion method
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Citations (4)

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JPS54152037A (en) * 1978-05-23 1979-11-29 Denki Kagaku Kogyo Kk Vulcanizable hot-melt adhesive and its production
JPH093423A (ja) * 1995-06-21 1997-01-07 Tosoh Corp 接着剤用ポリクロロプレンラテックス、その製造方法及びそれを用いた接着剤組成物
JP2011122141A (ja) * 2009-11-10 2011-06-23 Showa Denko Kk クロロプレン系重合体ラテックス及びその製造方法
JP5043423B2 (ja) * 2005-12-22 2012-10-10 昭和電工株式会社 クロロプレン系共重合体ラテックス、製造方法及びその用途

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JP3531749B2 (ja) * 1993-05-28 2004-05-31 電気化学工業株式会社 ポリクロロプレンラテックス及びその組成物
JP3718867B2 (ja) * 1994-05-09 2005-11-24 東ソー株式会社 接着剤用ラテックス及びそれを用いたクロロプレン系接着剤組成物
JP4491853B2 (ja) * 1998-07-31 2010-06-30 東ソー株式会社 スポンジ及びジャージ接着用クロロプレンゴムラテックス接着剤組成物
MY190746A (en) * 2016-09-02 2022-05-12 Denka Company Ltd Chloroprene rubber latex adhesive composition

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Publication number Priority date Publication date Assignee Title
JPS54152037A (en) * 1978-05-23 1979-11-29 Denki Kagaku Kogyo Kk Vulcanizable hot-melt adhesive and its production
JPH093423A (ja) * 1995-06-21 1997-01-07 Tosoh Corp 接着剤用ポリクロロプレンラテックス、その製造方法及びそれを用いた接着剤組成物
JP5043423B2 (ja) * 2005-12-22 2012-10-10 昭和電工株式会社 クロロプレン系共重合体ラテックス、製造方法及びその用途
JP2011122141A (ja) * 2009-11-10 2011-06-23 Showa Denko Kk クロロプレン系重合体ラテックス及びその製造方法

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Title
See also references of EP3985076A4

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CN113993963A (zh) 2022-01-28
CN113993963B (zh) 2023-07-28

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